Syntheses, characterization, crystal structure and antifungal activity of four tetraphenylphosphonium bis(N-R-sulfonyldithiocarbimato)zincate(II) salts

Four new compounds of the general formula: (Ph₄P)₂[Zn(RSO₂NCS₂)₂] where Ph₄P = tetraphenylphosphonium cation, R = 4-FC₆H₄ (1), 4-ClC₆H₄ (2), 4-BrC₆H₄ (3) and 4-IC₆H₄ (4), were obtained by the reaction of the appropriate potassium N-R-sulfonyldithiocarbimate (RSO₂NCS₂K₂) with zinc(II) acetate dihydrate in dimethylformamide. All compounds crystallize in the centrosymmetric space group of the triclinic system. The compounds 2, 3 and 4 are isostructural but compound 1 crystallizes as hemihydrate. The elemental analyses and the IR, ¹H NMR and ¹³C NMR data for 1-4 are consistent with the formation of bis(dithiocarbimato)zinc(II) complexes. These compounds are active against the phytopathogenic fungus Colletotrichum gloeosporioides.     

Syntheses, crystal structure and spectroscopic characterization of new platinum(II) dithiocarbimato complexes

The reaction of 4-iodobenzenesulfonamide or 4-fluorobenzenesulfonamide with CS₂ and KOH in dimethylformamide yielded the potassium N-R-sulfonyldithiocarbimates, K₂(RSO₂NCS₂) [R = 4-IC₆H₄ (1) and 4-FC₆H₄ (2)]. These salts reacted with K₂[PtCl₄] in water/methanol to yield complex anions bis(N-R-sulfonyldithiocarbimato)platinate(II), which were isolated as their tetrabutylammonium salts, (Bu₄N)₂[Pt(RSO₂NCS₂)₂] [R = 4-IC₆H₄ (3) and 4-FC₆H₄ (4)]. The structures of 2–4 were determined by X-ray crystallography. The Pt²⁺ in both complexes 3 and 4 lies at the inversion centre and the PtS₄ moiety has a distorted square-planar configuration. The compounds were also characterized by IR, ¹H NMR and ¹³C NMR spectroscopies, and elemental analyses. The molar conductance data are consistent with the fact that 3 and 4 are dianionic complexes.     

High-yield synthesis and characterization of 1,2-bis(p-vinylphenyl)ethane

The quantitative synthesis and complete characterization of 1,2-bis(p-vinylphenyl)ethane (p,p-BVPE) and its meta-, para-mixed isomers are reported. These crosslinkers copolymerize randomly with p-methylstyrene, leading to random crosslink distributions. The crosslinkers are prepared by Grignard coupling of (m,p)-vinylbenzyl chloride in tetrahydrofuran at low temperature to give the statistical mixture of m,m-, m,p-, and p,p-isomers in quantitative yield. Pure p-vinylbenzyl chloride is converted to pure p,p-BVPE. p,p-BVPE has also been separated from the mixture of isomers. The isomers are characterized by elemental analysis, mass spectrometry, ¹H-NMR, and ¹³C-NMR and by reversed-phase HPLC. © 1994 John Wiley & Sons, Inc.     

Syntheses, structural and spectroscopic characterization of novel zinc(II)-bis(trithiocarbimato) complexes and bis(N-methylsulfonyldithiocarbimate)-sulfide

Four zinc(II)-bis(trithiocarbimato) complexes with the general formula A₂[Zn(RSO₂NCS₃)₂] [A = Ph₄P⁺: R = CH₃ (1), 4-CH₃C₆H₄ (2); A = Bu₄N⁺: R = CH₃ (3), 4-CH₃C₆H₄ (4)] were obtained by the reaction of sulfur with the correspondent zinc(II)-bis(dithiocarbimato) complexes. Additionally, the compound (Ph₄P)₂[(CH₃SO₂NCS₂)₂S)] (5) was prepared from the potassium methylsulfonildithiocarbimate by oxidation with iodine. The compounds were characterized by elemental analyses and IR, ¹H NMR and ¹³C NMR spectroscopies. The compounds 4 and 5 were also characterized by X-ray diffraction techniques. The compound 4 crystallizes in the centrosymmetric space group C2/c of the monoclinic system. The Zn(II) is in a distorted tetrahedral environment (ZnS₄) in compound 4, and differ from the coordination mode observed in compound 1, which involves one sulfur and one nitrogen atom of each trithiocarbimate ligand. Compound 5 is the first example of a compound containing a bis(N-alkylsulfonyldithiocarbimate)-sulfide dianion and crystallises in the non-centrosymmetric space group P4₁2₁2 of the tetragonal system.     

Syntheses,crystal structures,and DNA-binding of some nickel(II) complexes of 1,3-bis(2-pyridylmethylthio)propane and pseudohalides

A series of neutral octahedral nickel(II) complexes of 1,3-bis(2-pyridylmethylthio)propane (L) and pseudohalide (X), formulated as [Ni^II(L)X₂] (where X?=?azide (1), cyanate (2), and isothiocyanate (3)), was synthesized. The complexes were characterized by physico-chemical and spectroscopic methods, and 1 and 3 also by single-crystal X-ray diffraction analyses. The structural study shows nickel in a distorted octahedral geometry comprised of the tetradentate NSSN ligand with trans pyridines and monocoordinated pseudohalides in cis positions. In dimethylformamide solution, the complexes had quasi-reversible Ni^II/Ni^III redox couples in cyclic voltammograms with E _1/2 values of +0.732, +0.747, and +0.815?V for 1, 2, and 3, respectively. To examine the biological activities of these complexes, interaction of 3 with calf thymus DNA was studied spectroscopically, showing groove-binding interaction.     

Syntheses and crystal structures of cobalt and nickel complexes of 2,6-bis(hydroxymethyl)pyridine

2?:?1 (L?:?M) Complexes of 2,6-bis(hydroxymethyl)pyridine (dhmp) with different Co(II) salts [CoCl₂·6H₂O, Co(SCN)₂, Co(NO₃)₂·6H₂O, CoSO₄·7H₂O and Co(OTos)₂·6H₂O] and Ni(II) salts [NiCl₂·6H₂O, Ni(NO₃)₂·6H₂O, NiSO₄·7H₂O and Ni(OTos)₂·6H₂O] have been prepared (1–9) and studied by infrared spectroscopy and X-ray crystallography. Influences on the distortion of the coordination polyhedron, the arrangement of the donor atoms and the packing structure of the complexes were investigated in terms of the different kinds of anions and cations. In the metal chloride Complexes 1 and 2, water of hydration was found, while in Complex 3 the counterion (SCN^–) acts as a ligand. The crystal structures of all complexes, except 3, show N₂O₄ hexacoordinated metal ions; in 3 the coordination environment is N₄O₂. Complex 1 is another exception in containing cobalt(III) instead of cobalt(II) as for the other complexes with cobalt salts. Logically, in Complex 1, one of the dhmp ligands is mono-deprotonated. In the neutral Complexes 2 and 4–9, the basal planes of the octahedra are made up of O donors and N atoms occupy the axial positions. In 1 as well as in 3, two N and two O atoms form the base, but in 1 O, and in 3 N atoms are on the axis of the coordination sphere. Moreover, the nickel Complexes 2, 5, 7 and 9 are more symmetrical in structure than the cobalt Complexes 1, 4, 6 and 8, in accordance with the Jahn–Teller effect. Packing structures of the complexes show specific interactions based on strong and weak H-bonds that involve the counterions, hydroxy groups and aromatic units, leading to extended network structures.     

Synthesis,structure, and antioxidative properties of a copper(II) complex with 1,2-bis(benzimidazol-2-yl)ethane ligand

1,2-Bis(benzimidazol-2-yl)ethane (bbe) and its copper(II) complex, {[Cu(bbe)Br₂]₂}·2DMF ( 1 ), have been synthesized and characterized by elemental analysis, ultraviolet–visible, and infrared spectra. The single crystal structure analysis of 1 shows two crystallographically independent but chemically identical [Cu(bbe)Br₂] molecules. The coordination geometry of the copper atoms may best be described as a distorted tetrahedron (τ₄ = 0.740 for Cu1 and 0.696 for Cu2). The cyclic voltammogram of complex 1 represents quasi-reversible Cu²⁺/Cu⁺ pairs. in vitro antioxidant tests showed that complex 1 has significant antioxidant activity against superoxide and hydroxy radicals. Photoluminescence investigations showed that the fluorescence intensity of complex 1 is significantly weaker than that of the ligand. This may be due to the paramagnetic effect of divalent copper to cause quenching of fluorescence.     

Crosslinking of styrene–butadiene rubber with 1,2-bis(benzocyclobutenyl)ethane

1,2-Bis(benzocyclobutenyl)ethane (BBCB) was used as a thermally activated crosslinking agent in styrene–butadiene rubber (SBR), both in the raw and carbon black-filled materials. Diels–Alder crosslinking reactions occurred to a significant degree, despite the lack of substituents of opposing electronic effects. The reaction is free of toxic crosslinking promoters and evolved by-products. Various physical properties such as ultimate elongation, tensile strength, and modulus were measured and compared to those properties of a sulfur-cured sample of SBR. Linear relationships were found between the amount of BBCB present and the modulus of the materials, as well as the amount of BBCB and solvent uptake in swell tests. © 1993 John Wiley & Sons, Inc.     

Syntheses and characterization of energetic compounds constructed from alkaline earth metal cations (Sr and Ba) and 1,2-bis(tetrazol-5-yl)ethane

Two new energetic compounds, [M(BTE)(H₂O)₅]_n (M=Sr(1), Ba(2)) [H₂BTE=1,2-bis(tetrazol-5-yl)ethane], have been hydrothermally synthesized and structurally characterized. Single-crystal X-ray diffraction analyses reveal that they are isomorphous and exhibit 2D (4,4) net framework, generated by 4-connected Sr₂(H₂O)₁₀/Ba₂(H₂O)₁₀ SBUs linked up by two independent binding modes of H₂BTE, and the resulting 2D structure is interconnected by hydrogen-bond and strong face to face π-π stacking interactions between two tetrazole rings to lead to a 3D supramolecular architecture. DSC measurements show that they have significant catalytic effects on thermal decomposition of ammonium perchlorate. Moreover, the photoluminescence properties, thermogravimetric analyses, and flame colors of the as-prepared compounds are also investigated in this paper.     

Reaction of dialkyl H-phosphonates with azines and 1,2-bis(tert-butylimino)ethane

Acetaldehyde and butyraldehyde azines and 1,2-bis(tert-butylimino)ethane add only one molecule of dialkyl H-phosphonate at room temperature to form alkyl (-aminoalkyl)phosphonates. IR spectra of compounds obtained are discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 2063–2065, August, 1996.     

Experimental vapor pressures of 1,2-bis(dimethylamino)ethane, 1-methylmorpholine, 1,2-bis(2-aminoethoxy)ethane and N-benzylethanolamine between 273.18 and 364.97 K

In this work, the experimental vapor pressures of four amines 1,2-bis(dimethylamino)ethane, 1-methylmorpholine, 1,2-bis(2-aminoethoxy)ethane and N-benzylethanolamine using a static apparatus are reported. The temperature range is comprised between 273.18 and 364.97 K and the pressure range between 0.782 Pa and 333 kPa. The molar enthalpies of vaporization at 298.15 K were calculated from Clausius–Clapeyron equation fitted on the experimental results.     

Synthesis,characterization, crystal structure and antiproliferative in vitro activity of long-chain aliphatic thiosemicarbazones and their Ni(II) complexes

In the course of a research on metal-based compounds active on white blood cell cancers (leukemia, lymphoma and myeloma) nine aliphatic thiosemicarbazones and their nickel complexes have been synthesized with the aim to test their effect on histiocytic lymphoma U937 cell proliferation. All compounds were characterized by elemental, IR and NMR spectra analyses and for five of the complexes also by X-ray crystallography diffraction analysis. Heptanal thiosemicarbazone and the corresponding nickel complex were chosen after a solubility/stability test to carry out preliminary experiments in vitro on human leukemia cell line U937. The complex possesses a remarkable biological activity in inhibiting cell growth and in inducing apoptosis.     

Synthesis and crystal structure of two novel nickel (imidazole) complexes having hydrogen-bonded networks

Two nickel (imidazole) complexes, Ni(im)₆Cl₂·4H₂O (1) and Ni(im)₆(NO₃)₂ (2) (im=imidazole) have been synthesized and characterized by elemental analysis, IR, UV, TG and single crystal X-ray diffraction. 1 crystallizes in the triclinic space group P-1 with a=8.800(6) Å, b=9.081(6) Å, c=10.565(7) Å, =75.058(9)°, β=83.143(8)°, γ=61.722(8)°, V=718.3(8) Å³, Z=1 and R₁ (wR₂)=0.0469 (0.1497). 2 crystallizes in the trigonal space group R-3 with a=12.370(6) Å, b=12.370(6) Å, c=14.782(14) Å, =90.00°, β=90.00°, γ=120.00°, V=1959(2) Å³, Z=3 and R₁ (wR₂)=0.0358 (0.0955). 1 and 2 exhibit different supramolecular network due to their different counter anions and different hydrogen bonding connection. In compound 1, [Ni(im)₆]²⁺ cation and counter anions Cl⁻ alternatively array in an ABAB fashion via N–HCl hydrogen bonding. In compound 2, the plane of each NO₃²⁻ is almost parallel and each NO₃²⁻ connect three different [Ni(im)₆]²⁺ cations via N–HO hydrogen bonding.     

Thermochromism in nickel(II) complexes: thermal, solid state H NMR and single crystal X-ray analysis of bis-(N,N-dimethyl-1,2-ethanediamine) nickel(II) perchlorate

The complex bis-(N,N-dimethyl-1,2-ethanediamine) nickel(II) perchlorate undergoes a first-order thermochromic phase transition at ca. 476 K, changing its color from orange to red. The room temperature X-ray crystal structure determination showed that the nickel ion possesses a square-planar geometry with two five membered chelate rings, in the δλ conformation, forming the NiN₄ chromophore. The broad-line ¹H NMR indicates the onset of a dynamic disorder of diamine chelate rings at the phase transition temperature region, while T₁ measurement of ¹H affords the activation energy of the puckering metal chelate rings to be 26 kJ mol⁻¹. The electronic spectrum revealed that a weakening of ligand field around the nickel is associated with the phase transition.     

Network diversity and supramolecular isomerism in copper(II)/1,2-bis(4-pyridyl)ethane coordination polymers

Reactions of copper(II) sources with 1,2-bis(4-pyridyl)ethane (bpe) yielded metal-organic networks with diverse topologies and dimensionalities. Compounds [Cu(bpe)₂(dmf)₂]_n(ClO₄)_2n·2ndmf (1·2ndmf), [Cu(bpe)₂(dmf)₂]_n(ClO₄)_2n·3.5ndmf (2·3.5ndmf), [Cu(bpe)₂(NO₃)₂]_n·2nH₂O (4·2nH₂O) and [Cu₂(bpe)(O₂CMe)₄]_n·0.7nH₂O (5·0.7nH₂O) have been isolated by altering the copper(II) source, the reaction solvent and the crystallization process. Compounds 1·2ndmf and 2·3.5ndmf consist of cationic [Cu(bpe)₂(dmf)₂]²⁺ repeating units assembled to 1D and 2D (4,4) networks, respectively, and represent supramolecular isomers due to the conformational isomerism of the bridging bpe molecules. Compound 4·2nH₂O consists of neutral mononuclear [Cu(dpe)₂(NO₃)₂] repeating units assembled to inclined interpenetrating (4,4) sheets describing an overall entanglement that is 3D in nature, and compound 5·0.7nH₂O consists of neutral dinuclear repeating units assembled to cross-linked 1D chains.     

Vibrational Spectroscopic Study of [1,2-bis(4-pyridyl)ethane]metal(II) Tetracyanonickelate(II). 2 m-Xylene Clathrates

Four new Hofmann-type clathrates of the form M(bpa)₂Ni(CN)_4· 2m-xylene (M = Mn , Fe , Co and Ni; bpa = 1,2-bis(4-pyridyl)ethane) have been synthesized and characterized by vibrational spectroscopy. The M(bpa)₂Ni(CN)₄ (M = Fe and Co) host structure is similar to the classical Hofmann-type host framework composed of layers of a two dimensional catena-metal tetra--cyanonickelate(II) network, but in M(bpa)₂Ni(CN)₄ (M = Mn and Ni), the Ni(CN)₄ moiety behaves as a bidentate –[NC-Ni(CN)₂-CN–]– unit in the host framework.     

Infrared Spectroscopic Study of Bis[1,2-bis(4-Pyridyl)ethane]cadmium(II) Tetracyanonickelate(II)-m-Xylene (1/2) Clathrate and Its Host Structure

Cd[1,2-bis-(4-pyridyl)ethane]2Ni(CN)4-m-xylene(1/2) clathrate and its host structure were prepared and characterized by chemical analysis and infrared spectroscopy. Vibrational assignments are proposed for the bands of the host lattice and guest molecules.     

1，2-二（3-甲氧基4-羟基苯基）乙烷的产生条件与表征

1,2-二(3-甲氧基-4-羟基苯基)乙烷(1,2-Bis(4-hydroxy-3-methoxyphenyl)ethane),又名亚乙基双愈创木酚(Ethylenediguaiacol),双香兰素(Divanillyl),结构如图1中副产物.较早的报道[1,2,3]是从原木素降解得到,具有抗氧化及抗肿瘤作用[4].